General Aspects of Isocyanide Reactivity

Mironov, Maxim A.

doi:10.1002/9783527652532.ch2

Cited by 22 publications

(18 citation statements)

References 122 publications

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“…38 This phenomenon has often been explained by invoking two different structures of isocyanide complexes, as depicted in Figure 10. 39 The bent structure (B) would require sufficient back-donation from the metal to the isocyanide π* orbital. Consistent with this bonding picture, the Co−C bond in 4a formed by the bent isocyanide is 0.04 Å shorter than the analogous bond in 3a formed by the linear isocyanide, and the corresponding CN bond in 4a is 0.03 Å longer than that in 3a.…”

Section: Synthesis and Structures Of Cobalt Pocop Pincermentioning

confidence: 99%

Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co₂(CO)₈: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System

Krause

Guan

2018

Organometallics

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A series of cobalt POCOP pincer complexes with the formulas {2,6-(iPr2PO)2-4-R′-C6H2}Co(CO)2 (R′ = H (1a), NMe2 (1b), OMe (1c), CO2Me (1d)), {2,6-(Ph2PO)2C6H3}Co(CO)2 (1e), and {2,6-(tBu2PO)2C6H3}Co(CO) (2f) have been synthesized through C–H bond activation of the corresponding pincer ligands with Co2(CO)8. These complexes have been demonstrated to catalyze the hydrosilylation of PhCHO with (EtO)3SiH, which exhibits an induction period and the decreasing reactivity order 1b > 1c > 1a > 1d > 1e. The catalytic protocol can be applied to various aldehydes with turnover numbers of up to 300. The CO ligands in the dicarbonyl complexes have been shown to exchange with 13CO at room temperature and partially dissociate from cobalt at high temperatures. Substitution of CO by tert-butyl isocyanide has been accomplished with 1a at 50–80 °C, resulting in the formation of {2,6-(iPr2PO)2C6H3}Co(CNtBu)(CO) (3a) and {2,6-(iPr2PO)2C6H3}Co(CNtBu)2 (4a). The catalytic reactions are more efficient when they are carried out in an open system or if the catalysts are preactivated by the aldehydes. The structures of 1a–e, 3a, and 4a have been studied by X-ray crystallography.

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Section: Synthesis and Structures Of Cobalt Pocop Pincermentioning

confidence: 99%

Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co₂(CO)₈: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System

Krause

Guan

2018

Organometallics

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“…Isocyanides easily undergo hydrolysis to formamides in the presence of acids. 54 Silica gel adsorbs water readily. Additionally, the hydroxyl groups on the surface of silica can catalyze the addition of water to isocyanide groups.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Isocyanides easily undergo hydrolysis to formamides in the presence of acids . Silica gel adsorbs water readily.…”

Section: Introductionmentioning

confidence: 99%

Semiheterogeneous Purification Protocol for the Removal of Ruthenium Impurities from Olefin Metathesis Reaction Products Using an Isocyanide Scavenger

Szczepaniak

Nogaś

Piątkowski

et al. 2019

Org. Process Res. Dev.

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A low-waste, time-economical, and scalable semiheterogeneous purification protocol for the removal of ruthenium residues from olefin metathesis (OM) reactions has been developed. It is based on the non-covalent immobilization of the commercially available isocyanide 1,4-bis(3-isocyanopropyl)piperazine (QA) on unmodified silica gel. The use of the heterogeneous scavenger QA@SiO 2 synthesized in situ during the purification process was shown to yield OM products with metal contamination usually below 5 ppm. Furthermore, the new purification protocol was effective on a gram scale in the ring-closing OM of an intermediate in the synthesis of cathepsin K inhibitors, leading to a product containing only 0.29 ppm Ru. Finally, QA was used in an aqueous medium and reduced the metal contamination from 9977 to 21 ppm.

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“…Since then, they have become valuable species in different fields, such as organic synthesis, coordination chemistry, or multicomponent reactions, among others. These isomers of cyanides present two resonant forms 1 and 1′ (Figure a) which are responsible for their rich reactivity; its terminal carbon atom can exist in a divalent state reacting either with nucleophiles, electrophiles, or radicals . The organometallic-mediated polymerization of isocyanides has been broadly studied, although much less attention has been devoted to its dimerization processes.…”

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confidence: 99%

“…These isomers of cyanides present two resonant forms 1 and 1′ (Figure 1a) which are responsible for their rich reactivity; its terminal carbon atom can exist in a divalent state reacting either with nucleophiles, electrophiles, or radicals. 5 The organometallic-mediated polymerization of isocyanides has been broadly studied, 6 although much less attention has been devoted to its dimerization processes. Isocyanides could react in a head-to-head manner toward the 1,4-diazabutatriene homodimers R−NCCN−R, but these species have never been isolated.…”

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In Search of 1,4-Diazabutatrienes, the Elusive Isocyanide Homodimers: The Superchameleonic F–NC

Marín‐Luna

Alajarı́n

2020

J. Org. Chem.

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General Aspects of Isocyanide Reactivity

Cited by 22 publications

References 122 publications

Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co₂(CO)₈: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System

Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co₂(CO)₈: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System

Semiheterogeneous Purification Protocol for the Removal of Ruthenium Impurities from Olefin Metathesis Reaction Products Using an Isocyanide Scavenger

In Search of 1,4-Diazabutatrienes, the Elusive Isocyanide Homodimers: The Superchameleonic F–NC

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General Aspects of Isocyanide Reactivity

Cited by 22 publications

References 122 publications

Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co2(CO)8: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System

Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co2(CO)8: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System

Semiheterogeneous Purification Protocol for the Removal of Ruthenium Impurities from Olefin Metathesis Reaction Products Using an Isocyanide Scavenger

In Search of 1,4-Diazabutatrienes, the Elusive Isocyanide Homodimers: The Superchameleonic F–NC

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Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co₂(CO)₈: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System

Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co₂(CO)₈: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System